EP3464655A1 - Method for extracting rare earth elements contained in permanent magnets - Google Patents
Method for extracting rare earth elements contained in permanent magnetsInfo
- Publication number
- EP3464655A1 EP3464655A1 EP17735187.1A EP17735187A EP3464655A1 EP 3464655 A1 EP3464655 A1 EP 3464655A1 EP 17735187 A EP17735187 A EP 17735187A EP 3464655 A1 EP3464655 A1 EP 3464655A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- iron
- grinding
- particles
- rare earths
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 89
- 229910052742 iron Inorganic materials 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 34
- 238000000227 grinding Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 27
- 238000004064 recycling Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- -1 air Chemical compound 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000002440 industrial waste Substances 0.000 claims description 3
- 235000010204 pine bark Nutrition 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000013019 agitation Methods 0.000 abstract description 2
- 238000007669 thermal treatment Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 238000004090 dissolution Methods 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229910052779 Neodymium Inorganic materials 0.000 description 11
- 229910052692 Dysprosium Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005347 demagnetization Effects 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001139 pH measurement Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000583 Nd alloy Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241001504639 Alcedo atthis Species 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 241001236212 Pinus pinaster Species 0.000 description 1
- 235000005105 Pinus pinaster Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a process for extracting rare earths contained in permanent magnets, in particular waste electrical and electronic equipment (D3E or WEEE).
- D3E or WEEE waste electrical and electronic equipment
- WEEE is the fastest growing waste stream, at 2-3% each year. They have a high recycling potential of the materials that compose them (ferrous and non-ferrous metals, rare metals, glasses, plastics ). These economic and environmental issues justified the establishment of a specific waste management system, based on the principle of extended producer responsibility (REP) for this equipment. Thus the collection and recycling of WEEE is operational in France since July 22, 2005 for professional WEEE, and since November 15, 2006 for household WEEE.
- REP extended producer responsibility
- rare earth permanent magnets found in many everyday objects, such as computers, televisions or mobile phones. These permanent magnets mainly contain neodymium (Nd) alloyed with iron and boron. They may also include dysprosium (Dy) and praseodymium (Pr).
- Document CN101817547 proposes to recover the rare earths of a magnet by a process consisting of crushing the magnet, adding to the powder obtained carbon and then putting this mixture in contact with a flow of chlorine gas to produce chlorides of rare earths and a volatile iron chloride. The rare earths are then purified by oxalic precipitation.
- WO 2009/119720 uses a process for immersing the rare earth alloy in a high temperature halogenated molten salt which makes it possible to extract the rare earths in the form of gaseous rare earth halides.
- a second mode of recycling implements a method of fusion.
- JP 2001 -335852 is based on the mixture of magnes powder and a fluorinated agent such as NH 4 F. The whole is heated until it is melted. The rare earths are found after cooling in mixture with a slag and can be separated by difference of density.
- JP 2010-199110 uses the same method of recycling by heating until melting and separation of the melted and unmelted fractions. This last fraction is rich in Nd alloy.
- the third mode of recycling is based on rare earth extraction by a molten metal.
- the method of document WO 2007/119846 uses the oxidation of magnets then the contact with molten aluminum leading to the formation of a rare earth oxide mixed with a slag and an alloy Fe-B that must be separated later.
- the difficulty lies in the delicate management of the aluminothermie reaction.
- Another process uses the strong affinity of magnesium fused with neodymium, unlike iron.
- the limits here are related to the management of a metal in the gaseous state, and to the energy expenditure that is associated with the process.
- This mode of treatment is not suitable for massive forms of magnets and is very expensive from an energy point of view.
- the aim of the invention is to propose an alternative method which does not have all or some of these disadvantages and which makes it possible to extract rare earths contained in permanent rare earth magnets, more particularly of the NdFeB type, doped or not, that is that is, added or not with other rare earths such as Dy and / or Pr.
- Permanent magnets are characterized by the fact that they have magnetic moments. Permanent magnets are magnets that have a remanence or persistence of their magnetic moments, that is to say, they retain their properties magnetic after the suppression of a magnetizing field.
- a permanent magnet is generally made of a hard magnetic material, manufactured, the remanent field and the coercive excitation are large. Permanent magnets almost always contain atoms of at least one of the following chemical elements: iron, cobalt or nickel, or the family of lanthanides (rare earths).
- Synthetic magnets used in the present invention are produced by sintering an alloy powder containing rare earth which then forms a polarized alloy under intense field of an electromagnet. Such materials are particularly used in the process according to the invention.
- NdFeB magnets are also known as neodymium magnets. They are composed mainly of an alloy of neodymium, iron and boron (Nd 2 Fei 4 B) to form a tetragonal crystalline system.
- Permanent magnets of NdFeB type when used in the process according to the invention can be contained in industrial waste originating, for example, from the recycling of hard disk drives of PC type central units or of portable computers, loudspeakers, for example mobile phones or computers, small electric motors or be composed of waste permanent magnet production.
- Such magnets are often surrounded by a layer of nickel. Nevertheless, their coating may be based on other metals such as cobalt, a copper-cobalt alloy, zinc, etc. The same process is applicable to magnets coated with epoxy.
- the subject of the invention is a process for extracting rare earths contained in a permanent magnet, more particularly of the NdFeB type, with or without added rare earths, comprising the steps of:
- the liquid phase contains more than 70% by mass of the rare earths of the permanent magnet having undergone the preceding steps of the process.
- the treatment beyond the Curie temperature that is to say at a temperature generally above 300 ° C., preferably between 300 and 400 ° C., and preferably around 350 ° C, allows the final demagnetization of the magnets, which is advantageous for the rest of the process which is not disturbed by the magnetic properties of the magnets.
- the heat treatment is carried out at a temperature below 600 ° C.
- this heat treatment is only intended for demagnetization. It is not intended to improve the dissolution of the metals in the solution containing the organic acid.
- the heat treatment is preferably carried out for a period of at least 10 minutes, and preferably between 10 and 40 minutes.
- grinding is meant fragmentation of the magnet by subjecting it to shock or pressure.
- the grinding stage makes it possible to obtain magnet powder, the particle size of which is selected so as to promote acid attack and dissolution of the rare earths. Indeed, the size of the particles influences the physicochemical properties of the substrate. The thinner the product, the faster the dissolution, but the manipulation of too fine powders can in some cases present disadvantages at various stages of the process.
- the grinding is a gentle grinding, for example decomposed in at least two grinding stages where the rejections of the first grinding are the subject of a second grinding as described in Figure 1:
- the sparing is practiced in order to obtain precisely the granulometry sought.
- the multi-stage grinding avoids the production of fine particles that volatilize, resulting in loss of material. In addition, it implies a lower energy expenditure than the grinding pushed.
- the sparing can be done in one step.
- the selection of the particles is carried out by sieving.
- the particles on which the acid attack is practiced have a size of less than 2 mm for 80% of them, and preferably for 90% of them.
- the particles on which the acid attack is performed have a size greater than 0.2 mm for 80% of them, and preferably for 90% of them.
- the particles on which the acid attack is performed have a size greater than 0.5 mm.
- the grinding is carried out using a shredder, for example a knife mill.
- the classification is carried out using sieves according to the standard methods.
- the heat treatment steps a) and b) grinding can be substituted by the supply of demagnetized particles having 80 to 90% of them less than 2 mm in size.
- Such particles may be from ground demagnetized magnets.
- the treatment of the particles with the solution containing an organic acid, or acid attack dissolves the constituents of the magnet and in particular the rare earths in the solution. It can also lead to a more or less partial dissolution of a coating present on the surface of the magnet. In the case of nickel-based coatings, the dissolution is very limited which makes it possible to separate it, in the form of a solid residue of nickel, at the end of the process.
- This attack is carried out with a solution of organic acid, in particular C1-C10, preferably C1-C5, carboxylic acids having at least one or two carboxyl functions (or radicals).
- organic acid in particular C1-C10, preferably C1-C5
- carboxylic acids having at least one or two carboxyl functions (or radicals).
- acetic acid, oxalic acid or citric acid, or a mixture thereof are acids which are particularly advantageous for use in the process according to the invention.
- the solvent of the acid is usually water.
- the acidic solution has a concentration ranging from 5 to 30% by volume, and for example a concentration of about 10%.
- concentration ranging from 0.8 to 2.4 M.
- the solution has a concentration of acetic acid greater than 1 M, and preferably 1.6 M. This can lead to total or partial dissolution of the magnet powders and an interesting partition between residual solid and solution of the different constituent elements of the permanent magnets.
- the magnet powder corresponding to particles selected at the end of the heat treatment and grinding steps is added to the acid solution at the rate of 150 g of powder per liter of d solution. 'acid.
- the acid attack is preferably carried out for a minimum of 1 hour, preferably less than 24 hours, more preferably ranging from 100 to 550 minutes, for example about 420 minutes.
- the acid attack (or leaching) is carried out at a temperature ranging from 10 to 50.degree. C., more preferably from 10 to 30.degree. C., and even more preferably at room temperature, that is to say 20.degree. vs. It can be performed under a static atmosphere of air or nitrogen, under air flow or under nitrogen flow.
- the acid attack brings the pH of the solution to a pH of less than 2.
- the amount of acid to be added is therefore advantageously an amount of acid to achieve such a pH.
- a low pH value increases the kinetics of the dissolution.
- the liquid phase containing the rare earths is then separated from the solid phase if not all the compounds of the powder have dissolved.
- This is for example the case for magnets surrounded by a layer of nickel, particularly in the presence of a solution of acetic acid.
- the nickel, associated or not with iron remains in solid form and can be recovered by simple solid / liquid separation.
- This solid / liquid separation can be carried out by any known method such as centrifugation, (for example at 3500 rpm for 10 minutes), filtration or decantation.
- At the end of the acid attack at least a portion of the ferrous fraction of the magnets is passed into solution.
- the iron is separated from the rare earths, optionally during an additional step.
- the iron can be precipitated while the rare earths remain, at least in part, in the liquid phase.
- oxygen can be introduced into the solution, for example by bubbling or stirring with an oxygen-containing gas, such as air, or pure oxygen.
- an oxygen-containing gas such as air, or pure oxygen.
- hydrogen peroxide H 2 0 2
- This mixture promotes the oxidation of iron from oxidation state 2 to degree 3 and thus the precipitation of iron III oxy-hydroxide compounds or oxy-hydroxides at low pH (ie at a pH generally below 4 ).
- the pH is preferably measured using a pH measurement resolution pH meter of 0.01 units, a resolution of the potential of 1 mV and a measurement resolution of 0.1 ° C, such as the Heitolab pH meter P310 of Heito.
- the electrode is Heito brand.
- the iron is thus precipitated and can be separated from the rare earths by a phase separation step such as filtration, centrifugation or decantation.
- a phase separation step such as filtration, centrifugation or decantation.
- the pH is kept below 4 by the addition of acid.
- the solution is maintained at a pH allowing the selective precipitation of iron.
- the pH is chosen between 3 and 4.
- the inventors have shown that the separation of iron is obtained by bringing the solution rich in rare earths and iron into contact with a material of biological origin such as oyster shell powder or powder. of pine bark.
- a material of biological origin such as oyster shell powder or powder. of pine bark.
- Many other biological materials are known to influence the behavior of metals in solution. This is for example the case of dried algae.
- oyster shell powder and pine bark powder have shown a particularly surprising efficiency for the reduction of iron compared to rare earths.
- calcined bone powder tends to trap all metals including iron and rare earths.
- These biological materials are advantageously used in the form of a fine powder.
- Such a powder may comprise essentially particles having a size of 0.5 to 5 mm, preferably 0.6 to 2 mm, for example 1, 25 mm.
- the iron separation step may be carried out prior to the liquid / solid separation described in step d) of the process, or following the liquid / solid separation and be followed by a second liquid / solid separation step .
- the rare earths extracted by this process are chosen from Nd, Dy and Pr, and a mixture thereof.
- the extraction process is carried out on magnets coated, for example with nickel, cobalt, a copper-cobalt alloy, zinc, epoxide or a mixture of these compounds.
- the subject of the invention is also a process for extracting rare earths contained in demagnetized particles originating from a permanent magnet, more particularly of the NdFeB type, with or without addition of other rare earths, the process comprising the steps of:
- the liquid phase advantageously containing more than 70% of the rare earths of the permanent magnet having undergone the preceding steps of the process .
- the conditions and steps of demagnetization, obtaining the particles, for example by grinding, the particle size, the treatment with an acid solution and the separation steps leading to the extraction of the rare earths may advantageously be such as those described herein. -before.
- the iron extraction steps can also be applied to this process.
- the invention also relates to a recycling process incorporating an extraction process according to the invention wherein the permanent magnet comes from industrial waste.
- the invention also relates to the products obtained directly from the process according to the invention and their subsequent use, in particular in the field of electronics.
- Another object of the invention is a method as described above comprising no chemical reaction steps between the steps of supplying demagnetized and ground magnet particles and the acid etching step.
- Another object of the invention is a process as described above not comprising chemical reaction steps between acid etching and solid / liquid separation and / or precipitation and / or iron fixation steps.
- Another object of the invention is a method as described in FIG. This method may incorporate one or more of the features described above.
- FIG. 1 schematizes the extraction method according to one embodiment of the invention of the rare earths present in permanent magnets, similar to the embodiments exemplified in Examples 2 to 4.
- FIG. 2a is a photograph taken under a scanning electron microscope (SEM) of a permanent magnet according to the control example 1.
- FIGS. 2b and 2c are the results of qualitative chemical analysis by scanning electron microscopy - energy dispersive spectroscopy (EDS SEM) carried out on the magnet of example 1, when it is displayed at the SEM.
- EDS SEM scanning electron microscopy - energy dispersive spectroscopy
- FIG. 3 shows the dissolution rates over time of Fe, Nd, Dy and Ni during the acid attack dissolution stage of a process according to the invention which is the subject of Example 2.
- FIG. 4 shows the dissolution rates according to the Fe, Nd and Dy time during the iron precipitation step of a process according to the invention which is the subject of Example 3.
- FIG. 5 shows the dissolution rates according to the Fe, Nd and Dy time during the iron precipitation step of a process according to the invention which is the subject of Example 4.
- FIGS. 2a to 2c show the SEM characterization results of a permanent magnet of the NdFeB type, without coating, which has not been subjected to the process according to the invention.
- the analysis makes it possible to highlight the granular structure of these magnets consisting of sintered Nd 2 Fei 4 B phase crystals (low arrow towards FIG. 2c) in the presence of an intergranular phase rich in rare earths (arrow up to FIG. 2b).
- FIG. 2c EDS SEM analysis of a sintered Nd 2 Fei 4 B phase crystal
- the emission lines of Nd, Pr and Dy are particularly identified.
- EXAMPLE 2 Extraction of rare earths from permanent nickel-coated magnets Samples of permanent magnets derived from portable or fixed computers (step 1 of the process schematized in FIG. 1) of the Neodymium-Iron-Bore (NdFeB) magnet type with nickel coating were used.
- the chemical composition of the NdFeB alloy component heart magnets is as follows: Iron 61, 3%, 35% neodymium, dysprosium 1, 8% and Boron 1, 4%.
- magnets were heat-treated for 20 minutes at a temperature of 350 ° C. in a muffle furnace, that is to say beyond their Curie temperature, with a view to definitively demagnetizing them (step 2 of FIG. process described in Figure 1), so as not to be disturbed in the following process by their magnetic properties.
- the samples were ground so as to obtain a particle size of less than 2 mm.
- step 4 The refusal to sieve, that is to say the particles whose particle size was greater than the desired particle size were subjected to a second grinding step (step 4). This grinding in two stages is a gentle grinding.
- Steps 3 and 4 of Figure 1 were carried out using a shredder-type mill (RETSCH SM100 type knife mill - from Retsch GmbH, Retsch-Allee 1 -5, 42781 Haan, Germany) with a 2 mm sieve.
- Particles larger than or equal to 2 mm then underwent a second milling step using the same mill with a 2 mm sieve.
- the powder was automatically classified on the 2 mm sieve, resulting in a powder such that 100% of the particles were smaller than 2 mm (quartile 10 or d100).
- the supernatant was then filtered through a 0.22 ⁇ syringe filter (step 6), so as to separate the solid phase from the liquid phase.
- the resulting metal solutions were then subjected to atomic absorption analysis to determine the concentration of the different dissolved metals.
- the iron was precipitated. This precipitation was carried out by placing the solution in the presence of oxygen which is introduced into the solution by bubbling air.
- the pH was adjusted to a pH ranging from 3 to 4 by adding a additional amount of acetic acid to selectively precipitate iron III without precipitating the rare earths.
- the pH measurement was carried out using a Heito brand pH meter and model P 310, associated with a Heito electrode.
- Example 3 A magnet powder identical to that used in Example 2 was treated in the same manner as in Example 2, except that the acid treatment step was carried out under nitrogen and the separation of iron from the soil. Rare has not been done by the presence of oxygen.
- the rare earth metal solutions obtained after dissolution by acid attack were treated with materials of biological origin which make it possible to optimize the separation of rare earths and iron.
- FIG. 4 The results of the atomic absorption analysis of Fe, Nd and Dy concentrations present in the successive samples taken over time during this precipitation step are presented in FIG. 4.
- This figure shows that iron (low curve), the Nd (upper curve) and the Dy (intermediate curve) are fixed by the bark powder in different proportions from each other. Iron is removed from the solution in its entirety, while less than 50% of the rare earths are. This process makes it possible to capture, and thus to separate, Fe, from the solution, thus making it possible to extract the iron from the solution and to keep a large part of the rare earths in solution.
- FIG. 5 The results of the atomic absorption analysis of Fe, Nd and Dy concentrations present in the successive samples taken during the time during this precipitation step are presented in FIG. 5.
- This figure shows that the iron (low curve), the Nd (upper curve) and the Dy (intermediate curve) are fixed by the oyster shell powder in different proportions from each other. Iron is removed from the solution (precipitate) in its entirety, while less than 35% of the rare earths are. This process makes it possible to capture, and thus to separate, Fe, from the solution, thus making it possible to extract the iron from the solution and to keep a large part of the rare earths in solution.
- the invention is not limited to the embodiments presented and other embodiments will become apparent to those skilled in the art.
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Abstract
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FR1655059A FR3052171B1 (en) | 2016-06-03 | 2016-06-03 | PROCESS FOR EXTRACTING RARE EARTHS CONTAINED IN PERMANENT MAGNETS |
PCT/FR2017/051399 WO2017207947A1 (en) | 2016-06-03 | 2017-06-02 | Method for extracting rare earth elements contained in permanent magnets |
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EP3464655A1 true EP3464655A1 (en) | 2019-04-10 |
EP3464655B1 EP3464655B1 (en) | 2022-05-25 |
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US (2) | US11155898B2 (en) |
EP (1) | EP3464655B1 (en) |
CA (1) | CA3022190C (en) |
DK (1) | DK3464655T3 (en) |
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FR3064496A1 (en) * | 2017-03-31 | 2018-10-05 | Centre National De La Recherche Scientifique | USE OF NATURAL MATERIALS OF VEGETABLE ORIGIN RICH IN PHENOLIC ACIDS FOR THE IMPLEMENTATION OF ORGANIC CHEMICAL REACTION AND RECYCLING OF CATALYSTS |
IT201800005178A1 (en) * | 2018-05-08 | 2019-11-08 | Hydrometallurgical process for the treatment of permanent magnets | |
CN108823436A (en) * | 2018-07-05 | 2018-11-16 | 武汉工程大学 | A kind of compound leaching agent of the formates of weathered superficial leaching rare-earth ore |
EP3715482A1 (en) * | 2019-03-29 | 2020-09-30 | Tata Consultancy Services Limited | Method and system for separation of rare earth elements from secondary sources |
FR3121686B1 (en) * | 2021-04-09 | 2023-11-10 | Brgm | Process for the selective extraction of rare earths in the form of oxides |
EP4177365A1 (en) * | 2021-11-05 | 2023-05-10 | Commissariat à l'Energie Atomique et aux Energies Alternatives | A green process for the extraction of lanthanide elements |
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US5362459A (en) | 1993-05-17 | 1994-11-08 | Pure-Etch Co. | Neodymium recovery process |
US5429887A (en) * | 1994-05-16 | 1995-07-04 | The United States Of America As Represented By The Secretary Of The Interior | Process for treating AB5 nickel-metal hydride battery scrap |
US5728355A (en) * | 1995-09-27 | 1998-03-17 | Santoku Metal Industry Co., Ltd. | Method for recovering reusable rare earth compounds |
JP2001335852A (en) | 2000-05-25 | 2001-12-04 | Shin Etsu Chem Co Ltd | METHOD FOR RECOVERING Nd-BASED RARE EARTH MAGNET ALLOY WASTE POWDER |
WO2003078671A1 (en) * | 2002-03-19 | 2003-09-25 | Santoku Corporation | Method for recovering useful element from rare earth - transition metal alloy scrap |
CN1255560C (en) * | 2004-06-28 | 2006-05-10 | 辽宁美宝稀土材料有限公司 | Process for recovering rare earth from neodymium-ion-boron waste materials |
KR100578712B1 (en) * | 2004-11-04 | 2006-05-12 | 한국지질자원연구원 | Recovery of Neodymium from NdFeB Oxidation-Roasted Scrap by Acetic Acid Leaching |
MY144466A (en) | 2006-04-17 | 2011-09-30 | Santoku Corp | Method of recovering useful materials from scrap of rare earth-iron-boron magnet |
CN102046820B (en) | 2008-03-26 | 2013-07-10 | 财团法人生产技术研究奖励会 | Method and apparatus for collection of rare earth element |
JP4820423B2 (en) | 2009-02-23 | 2011-11-24 | 有限会社レアメタルズ21 | Method of recovering neodymium magnet from used equipment and neodymium magnet recovered or recycled by the method |
CN101817547B (en) | 2010-05-07 | 2011-10-05 | 沈阳工业大学 | Method for recovering mixed rare earth chlorides from neodymium iron boron permanent magnet material scraps |
FR2997095B1 (en) * | 2012-10-24 | 2014-11-28 | Commissariat Energie Atomique | METHOD FOR ISOLATING RARE EARTHS AND / OR APPROPRIATE METAL ELEMENT (S) CONTAINED IN THE MAGNETIC PHASE OF PERMANENT MAGNETS. |
US9376735B2 (en) * | 2013-03-15 | 2016-06-28 | University Of Houston System | Methods and systems for recovering rare earth elements |
US10577677B2 (en) * | 2015-07-10 | 2020-03-03 | University Of Houston System | Process for the recovery of rare earth metals from permanent magnets |
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US20210363608A1 (en) | 2021-11-25 |
FR3052171A1 (en) | 2017-12-08 |
WO2017207947A1 (en) | 2017-12-07 |
CA3022190C (en) | 2023-10-10 |
FR3052171B1 (en) | 2021-01-01 |
DK3464655T3 (en) | 2022-07-18 |
US11155898B2 (en) | 2021-10-26 |
US20190169710A1 (en) | 2019-06-06 |
EP3464655B1 (en) | 2022-05-25 |
CA3022190A1 (en) | 2017-12-07 |
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